o-(diloweralkoxythiophosphinylthioalkyl)phenyl n-loweralkyl carbamates



United States Patent Ofiiice 3,331,894 Patented July 18, 1967 This invention relates to novel compositions of matter and to methods for pest control utilizing said compositions. More specifically, the invention relates to novel N-lower-alkyl-substituted carbamates of thioalkylphenols.

The novel compositions of the present invention are represented by the following formula wherein the substituent X is a substituted or an unsub stituted alkylene radical having at least two carbon atoms, said alkylene radical preferably having from 3 to 8 carbon atoms, the sulfur atom attached to said alkylene radical being separated from the phenyl ring by at least two carbon atoms, preferably by 3 to 8 carbon atoms, R R and R are substituents individually selected from the group consisting of hydrogen and lower alkyl radicals, R is a substituent selected from the group consisting of hydrocarbyl and acyl, p is an integer from to 2, inclusive, p being 0 when R is acyl and n is an integer from 1 to 2, inclusive, preferably 1.

The term lower alkyl is meant to encompass alkyl radicals having from 1 to about 6 carbon atoms, said radicals being branched or unbranched.

'For reasons of cost and the like, the lower alkyl radical on the carbamate nitrogen is preferably methyl.

The term acyl as used herein refers to the radical obtained by removal of the OH group from an acid.

The term hydrocarbyl as used herein represents the radical obtained by removal of the hydrogen atom from a hydrocarbon and thus encompasses alkyl, alkenyl, cycloalkyl, phenyl, naphthyl, alkylphenyl, benzyl, and other arylalkyl. The preferred hydrocarbyl radicals are those having from 1 to about 20 carbon atoms.

The alkylene group X may be unsubstituted or may be substituted by lower alkyl, hydrocarbyloxymethyl, hydrocarbylthiomethyl, hydrocarbyloxy, Z-(hydrocarbyloxy)ethyl, or 2-(hydrocarbylthio)ethyl.

The compositions of the present invention are useful for their insecticidal activity toward a large variety of insects (including mites) and against other invertebrate animal pests such as spiders, millipedes, slugs, and nema todes. The compositions of the invention also have unusual repellent properties toward various inspects. Further, the compositions of the present invention have useful systemic properties in plants, i.e., the ability to translocate from the site of application to other parts of the plant where insects are located.

Illustrative examples of the X substituents include CH CH CH CH CH CH(CH )CH CH CH (CH CH(CH CH (CH,

CH (CH CH CH CH CH (C H CH CH (CH SC H CH CH CH (CH OC H CH CH CH (CH OCH CH CH CH (CH SCH CH CH CH (CH CH SCH CH CH CH(CH OCH CH CH (CH CH CH OCH and the like.

Illustrative examples of the substituents R R and R include hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-amyl, l-methylbutyl, isoamyl, tert-amyl, l-ethylpropyl and hexyl. It is to be appreciated that the substituent X can be other lower alkyl groups without departing from the scope of the instant invention.

Illustrative examples of the R substituents include alkyl groups, such as methyl, ethyl, propyl, isopropyl, n-bntyl, isobutyl, sec-butyl, tert-butyl, amyl, hexyl, cyclohexyl, octyl, nonyl, decyl, dodecyl, octadecyl, and eicosyl also substituted alkyl such as allyl, methoxyethyl, hydroxyethyl, chloropropyl. Further, the R substituent can be aryl, such as phenyl, tolyl, tert-butylphenyl, p-chlorophenyl, 2,4,S-trichlorophenyl, or arylalkyl such as benzyl, 2-phenylethyl, p-chlorobenzyl, o-methoxybenzyl, or acyl such as acetyl, propionyl, butyryl, benzoyl, thiobenzoyl, cyano, N-methylcarbamoyl, N-methylthiocarbamoyl, N,N-dirnethylcarbarnoyl, N,N-dimethylthiocarbamoyl, other N- and N,N-hydrocarbyl-substituted carbamoyl and thiocarbamoyl, dimethoxyphosphenyl, di ethoxyphosphenyl, dimethoxythiophosphenyl, diethoxythiophosphenyl, other di(lower alkoxy)phosphinyl and thiophosphinyl and O-alkylthio-carbonyl.

It is, of course, appreciated that the substituent X can be other hydrocarbyl and acyl groups without departing from the scope of the instant invention.

For reasons for high pesticidal activity and ease of manufacture by applicants copending process of SN. 262,375, filed Mar. 4, 1963 certain species are preferred. The preferred group is encompassed by the formula:

0 CONHCHa -OHCHZGH2SO R t, R R

wherein the substituents R R and R are as above defined, R is a substituent selected from the group consisting of hydrogen, lower alkoxy-methyl, and 2-(loweralkoxy)ethyl, and R is a substituent selected from alkyl, phenyl, benzyl, acetyl, and di(lower alkoxy)thiophosphinyL'p being an integer from to 2 when R is selected from phenyl, benzyl, and alkyl, and p being 0 whenR is selected from acetyl and di(lower alkoxy)thiophosphinyl. The preferred alkyls, as already mentioned above, have from 1 to 20 carbon atoms.

Examples of compounds of this preferred group are those of the detailed examples given below as well as the following:

2 (3 -methylthiopropyl) -3-methyl-5-isopropylphenyl N-methyl carbamate;

2 B-methylthiopropyl) -5-tert-butylphenyl N-methyl carbamate;

2 (3 -methylthiopropyl)-5-(1-ethylbuntyl)phenyl N-methyl carbamate;

2- 3 -methylthiopropyl) -3,4,5-trimethylphenyl N-methyl carbamate;

2- (3-methylthio-1- [ethoxymet-hyl propyl) phenyl N-methyl carbamate;

2- 3-methylthio-l- [hexyloxymethyl] propyl) phenyl N-methyl carbamate;

2-(3-isopropylthio-l-[Z-butoxyethyl] propy l) phenyl N-methyl carbamate;

2(3-octylsulfinylpropyl) phenyl N-methyl carbamate;

2-(3-octadecylsulfonylpropyl) phenyl N-methyl carbamate;

2-(3-diamyloxythiophosphinylthiopropyl) phenyl N-methyl carbamate; and

2- 3-phenylsulfonylpropyl) -4-methylphenyl N-met-hyl carbamate.

The N-methylcarbarnates of the present invention are prepared from the corresponding phenols by (1) reaction with methyl isocyanate, (2) reaction with methylcarbamyl chloride (preferably in the presence of one molar equivalent of an HCl-acceptor such as caustic soda, triethylamine, or the like, or (3) reaction with phosgene to form the chloroforrnate, followed by reaction with methylamine to replace the chlorine .atom.

The composition of the present invention wherein the integer p is 1 or 2 may be thus made from the corresponding phenols, in which case no further reaction step is necessary, or may be made from the less oxidized phenol sulfide having a lower value of p, in which case the required additional oxygen atoms are replaced on the sulfur after carbamylation by subsequent oxidation by one or two molar equivalents (as required) of a suitable sulfide oxidizing agent, for example, hydrogen peroxide, peracetic acid, performic acid, perbenzoic acid, chromic acid,

or molecular oxygen in the presence of a catalyst (such While the compositions of the instant invention maybe utilized as pesticides in the pure form, they may be conveniently employed in the form of formulations which,- in many instances, enhance pesticidal activity. Suitable formulations include solutions of the pesticide composition in solvents such as petroleum hydrocarbons, tag,

xylene, heavy aromatic naphthalenes and the like, and aqueous dispersions or emulsions generally containing surface active agents such as those listed in Soap and Chemical Specialties, volume 3, No. 7, pages 50-61, No. 8, pages 4861, No. 9, pages 5267,'and N0. 10, pages 38-67 (1955). Also useful are solid formulations of the compositions of the instant invention. For example, solid carriers such as talc, silica, clay, vermiculite and the like may be utilized in the formulation. The solid formulations may also contain surface active agents, sticking agents, stabilizing agents, or binders to facilitate their application.

The composition of the present invention may further be formulated with other pesticides, for example, fungicides, such as sulfur, the fungicidal dithiocarbamates,

dodecyl guanidine, nitropolychlorobenzenes and various fungicidal compositions containing chlorinated alkyl thio groups, such as captan. Further, the compositions of the present invention may be formulated with other insecti cides and acaricides, such as DDT, lindane, methoxychlor, parathion, methyl parathion, malathion, sulfur, pyrethrins, bis(pentachlorocyclopentadienyl), other chlorinated insecticides, phosphate insecticides and the like.

Further, the compositions of the present invention may be formulated with synergists that serve to enhance the pesticidal activity, for example, piperonyl butoxide and the like. It is, of course, appreciated that anypesticidal,

composition may be used in combination with the compositions of. the present invention which may serve to enhance, complemenhor synergize said compositions.

The method of using these pesticides is to apply them to the locus of the pests to be controlled, preferably at rates of about 0.05 to 20. pounds of active ingredient per acre in the case of surface application to crops, or when admixed with a medium such as soil, water, or air, con- Example 1.0*(3-methylthi0pr0pyl)phenyl N -mrethy lcarbamale A mixture of 2.2 parts of o-(3-methylthiopropyl)- phenol, prepared as described in applicants application S.N. 262,375 filed on even date herewith, 1 part of methyl isocyanate and 0.01 part of dibutyl tin dilaurate catalyst was allowed to stand at 35 C. for 5 hours, then stripped free of unreacted isocyanate by applying a vacuum of 0.1 millimeters of mercury pressure at to C. for 1 hour. The product was obtained as a residual oil, nearly colorless andmoderately viscous, exhibiting the characteristic carbamate infrared absorption bands at 5.8 mi crons (carbonyl) and 3 microns (NH). On standing, the oil solidified to a crystalline solid, melting point 38 to 40 0., having the correct nitrogen analysis for CIZHI'IOZNS Examples 2 to 27 Substantially the procedure of Example 1 was followed, with minor, modifications in regard to temperature, time and use of solvent, In all cases, a catalytic amount, 0.1 to. 1 percent, of dibutyl tin dilaurate was employed. The conditions of the reactions and the properties of the products obtained thereby are presented in the following tables. 1

C HsNC Analysis Example Phenol Used Used Reaction Reaction Description (and parts Empirical N 0. (parts by weight) (parts by Temp., Time, by wt.) or N-methylcar- Formula weight) C. hrs. bamate obtained N N Calcd. Found 2 o-(3ecetylthiopropyl) phenol 2 Reflux Viscous straw colored oil CraHnOaNS 5.25 5.06

(5.3). .7 3 o-(diethoxythiophosphinylthio- 2 Reflux Viscous reddish oil (6.0) clarinomszr 3. 72 3.2

propyl) phenol (5.25). 4 O-(S-ethylthiopropyl) phenol (5) 2 40 18 Cl(ear)ncarly colorless 011 CrzHmOaNS 5.4 5.0

5.5 5 o-(3n-butylthiopropyl) phenol 2 40 18 do C15H230 NS 4. 97 4. 71 6 o-(3-tert-butylthiopropyl) 2 40 18 Colorless crystals, M.P. CisHzsOzNS 4. 97 5.17

phenol (5). 67 (from hexane) (5.5). 7 o-(3n-octylthiopropyl) phenol 2 40 18 Light amber oil (5.5) CwHarOzNS 4. 50 4. 00 8 o-(3-benzylthiopropyl) phenol 2 40 18 Clear viscous syrup (5)...- C1 H O NS 4.44 4.12 0 o-(S-(lodecylthiopropyl) phenol 2 40 18 Clear oil (5.2) CZEHQQOZNS 3. 56 3.39 10 o(3-phcnylthiopropyl) phenol 2 40 18 Cl(eag)light amber syrup CuHmOzNS 4. 64 4. 35

. 5. 11 ..1 o (3-methylthiopropyl)-p-cresol 1. 5 35 18 Colorless crystals, M.P. CraHieOzNS 5. 5 6.0

(2.57). 53.554.5, (from hcptane benzene) (2). 12 2,6-di(3methylthiopropyl) phenol 2 30 18 Colorless oil (5.3) CwHzaOzNSa 4.3 4.7

.5 13 o-(3-niethylthiobutyl) phenol 1. 5 30 I8 Cogogess viscous syrup CraHmOzNS 5. 5 5. 1

2.2 14 0 (Ii-methylthiopropyl-m-cresol 2 25 12 do CHHWOZNS 5. 5 6. 7 15 2- (3-methylthiopropyl)3,5-xylenol 2 25 12 Colorless viscous syrup C12HmO2NSCl 5.12 5.01

l l6 2-(3 methylthiopropyl)-4-chloro- 5 25 12 Colorless crystals, M.P. C12H1GO2NSCI 5.12 5.01

phenol (0). 65G6 (from benzene heptane) (5). 2-(3-methylthiopropyl) 3,5-diiso- 1O 25 12 Clear viscous syrup (7) CraHzeOzNS 4.3 4.3

propylphcnol (6). o-(3Incthylsu lfinylpr0pyl)phenol 3 25 12 Viscous tan H2O sol. C12H110aNS 5. 49 5. 87

(5.97). syrup (7.5). o-(B-ethylsulfinylpropyl)phenol 2 25 12 Viscous colorless syrup CuHmOsNS 5. 21 4. 92

(4 plus 10 parts benzene). (3.1). 0-(3-n-butylsulfinylpropyl) phenol 2 25 12 do C HnO NS 4. 71 4. 61

(3 plus 10 parts benzene). o-(3-octylsultinylpropyl)phenol 1 25 12 Viscous colorless syrup CrrHarOaNS 3. 9 4.0

(6.7 plus 50 parts benzene). 22 o-(3-phenylsulfinylpropyl) phenol 1 25 12 Viscous colorless syrup CnHwOaNS 4. 42 4. 82

(7.8 plus 5 parts benzene). .8 23 o-(3-methylsulionylpropyl) 3 25 12 Brownish viscous syrup C1ZH1O4NS 5. 2 5. 5

phenol (5 plus 10 parts benzene). 24 o-(3-1nethylsulfinylpropyD-p- 5 25 48 Viscous yellowish syrup CnHnOaNS 5. 21 5.12

cresol (10 plus benzene). v (10.5). o-(2-methylthiopropyl) phenol (7). 5 25 12 Viscous colorless syrup C12H1702NS 5. 81 5.71 26 o-(lilmetliyl-7methylthi0heptyl) 5 25 12 .d0 CuHzrOzNS 4. 51 4. 61

p eno l0 27 o(3-methylthio-1-[mcthoxymeth- 5 25 12 Viscous amber syrup C H10 NS 4.9 4.5

yl]propyl) phenol (10).

Example 28-Miticirlal activity Bean plants (tendergreen variety) infested with about 100 mites per leaf (adult two-spotted mites or" Tetranychus spp.) were sprayed with 0.1 percent aqueous dispersions of the various test chemicals. After 24 hours, the percentage mite kill was observed, with the following results:

Chemical: Percent mite kill o-(3 methylthiopropyl) phenyl N-methylcarbamate (82 at 0.01 percent) 100 o-(3-methylthio l-[methoxymethyl] phenyl N- methylcarbamate 100 o-(diethoxythiophosphinylthiopropyl) phenyl N- methylcarbamate 100 o-( 3 octylthiopropyl) phenyl N methylcarbamate 100 o-(3-dodecylthiopropyl) phenyl N-methylcarbamate 100 o-(3-phenylthiopropyl) phenyl N methylcarbamate 95 o-(3 acetylthiopropyl) phenyl N-methylcarbamate 40 o-(methylthio) phenyl N-methylcarbamate 1 0 F01' comparison.

Example 29Aphicidal activity Nasturtium plants heavily infested with aphids (Aphis fabae) were sprayed with 0.1 percent aqueous dispersions of the various compounds. After 24 hours, the percentage l ill was observed.

Also percent kill when same amount of chemical was dispersed in the soil in which the nasturtiuins were rooted. (Systemic test.)

Even at 0.025 percent concentration o-(3-methylthiopropyl)phenyl N-methylcarbamate continued to give 100 percent kill, whereas o-(methylthio) phenyl N-methylcarbamate gave only 42 percent kill of Aphis fabae.

Example 30-H0usefly control Various compounds of the invention were sprayed as 1 percent, and 0.1 percent aqueous dispersions onto caged houseflies. (Musca domestica.) At 2 hours and 24 hours after spraying, the effect was observed, with the following results:

Chemical Observatin* At 1 At 0.1

percent percent o-(3-dimethoxythiophos- 2 hr. KD 100 100 phinylthiopropyl) phenyl 24 hrs. kill 100 100 N-methylcarbamate.

o-(3-methylthiopropyl) 2 hr. KD 100 95 phenyl N- 24 hr. kill- 100 85 methylcarbamate.

o(B-ethylthiopropyl)phenyl 2 hr. KD 100 65 N-methylcarbamatc. 24 hr. kill. 100 100 o-(3-n-butylthiopropyl) 2 hr. KD 100 95 phenyl N-v 24 hr. kill 100 95 methylcarbamate.

o-(3-n-octylthiopropyl) 2 hr. KD 100 35 phenyl N- 24 hr. kill- 100 60 methylcarbamate.

o-(3-pheny1thiopropyl) 2 hr. KD 100 45 phenyl N- 24 hr. kill. 100 70 methylcarhamate.

o-(3-bcnzylthiopropyl) 2 hr. KD 100 85 phenyl N- 24 hr. kill. 100 90 methylcarbamate.

o-(3-tert-butylthiopropyl) 2 hr. KD 100 55 phenyl N- 24 hr. kill. 100 80 methylcarbamatc.

2-(3-methylthiopropyl) 2 hr. KD 75 0 phenyl N- 24 hr. kill 85 75 methylcarbamate.

2-(3-ethylsulfinylpropyl) 2 hr. KD S5 0 phenyl N- 24 hr. kill 95 30. methylcarbamate.

2-(3-methylthi0propyD-3,5- 2 hr. KD 100 100 dimethylphenyl N 24 hr. kill. 100 100 methylcarbamate.

*KD =knock down.

The-compositions of the invention also show repellency toward some insect species as demonstrated by the following example:

Example 31Insect repellency Leaves of bean plants infested with Mexican bean beetle- Example 32 An emulsifiable concentrate was prepared by blending the following ingredients:

Pounds Carbamate product of Example 1 2.0 Emcol H300X 1 0.1 Emcol HSOOX 1 0.1

Xylene to total volume of 1 gallon.

1 Commercial emulsifiers manufactured by Witco Chemical Company: blends of alkylaryl sulfonate salts with polyoxyethylene ethers.

This concentrate was emulsified with water prior to application to lima bean plants with aphid control.

Example 33 A wettable powder formulation was prepared by blending and grinding together the following ingredients in a hammer mill:

Pound Carbamate product of Example 2 1.00 Sorbit P (alkylarylsulfonate wetting agent) 0.0 5 Marasperse N(lignin sulfonate dispersing agent) 0.05 Microcel E (synthetic silicate carrier) 0.90

The resultant powder was dispersed in water by gentle agitation before spraying onto cotton plants for general insect control.

While there have been described various embodiments of the invention, the methods and elements described 8 are not intended to be understood as limiting the scope of the invention, as it is realized that changes therein are possible, and it is further intended that each element recited in any of the following claims is to be understoodv as referring to all equivalent elements for accomplishing substantially the same results in substantially the same or equivalent'manner, it being intended to cover the invention broadly in whatever form its principle may be utilized.

We claim:

1. A compound of the formula wherein n is an integer from 1 to 2, wherein the substituent X is an alkylene group of from 2 to 8 carbon atoms, R R and R are substituents selected from the group consisting of hydrogen and lower alkyl, R is di(lower alkoxy) thiophosphinyl and the sulfur atom is separated from the phenyl ring by at least two carbon atoms.

2. A compound of the formula wherein the substituent X is an alkylene group of from 3 to 8 carbon atoms, R R and R are substituents se- 1 lected from the group consisting of hydrogen and lower alkyl, R'is di(lower alkoxy) thiophosphinyl and the sulfur atom is separated from the phenylv ring by at least three carbon atoms.

3. A compound of the formula O-CONHCHa CHCHzCHzSR References Cited UNITED STATES PATENTS 2,870,186 1/1959 Orlotf et al 260461 2,929,833 3/1960 Orloff et al 260-461 3,060,088 10/1962 Kings'bury et a1. 16753 3,094,457 6/1963 Birum l67-30 3,114,673 12/1963 Lemin l67-30 FOREIGN PATENTS 912,895 12/ 1962 Great Britain.

CHARLES B. PARKER, Primary Examiner.

JULIAN S. LEVITT, Examiner.

Gr. A. MENTIS, F. M. SIKORA, A. H. SUTTO,

Assistant Examiners. 

1. A COMPOUND OF THE FORMULA 